Carbamoyloxyimino-azolidines as molluscicides

ABSTRACT

Compounds of the formula   WHEREIN Q is sulphur, sulphoxide, sulphone or oxygen; R1 and R2 which may be the same or different are hydrogen or alkyl containing up to four carbon atoms; R3 is hydrogen, alkyl containing up to eight carbon atoms, allyl, benzyl, dimethylamino, methyl-thiomethyl, ethoxy-carbonylmethyl, or halosubstituted pyridyl; and either (i) X is a group of the formula:   where R4 and R5, which may be the same or different, are hydrogen, alkyl containing up to four carbon atoms, phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl; and Y is oxygen, sulphur or alkylimino containing up to four carbon atoms; or (ii) Y is a group of the formula:   where R4 and R5, which may be the same or different, are hydrogen, alkyl containing up to four carbon atoms, phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl; and X is oxygen, sulphur or alkylimino containing up to four carbon atoms; useful as pesticides.

States atent [191 Punja [451 Sept.9,1975

[ CARBAMOYLOXYIMlNO-AZOLIDINES AS MOLLUSCICIDES [75] Inventor: Nazim Punja, Wokingham, England [73] Assignee: Imperial Chemical Industries Limited, London, England [22] Filed: Dec. 18, 1974 [21] App]. No: 534,135

Related US. Application Data [62] Division of Ser. No. 478,043, June 10, 1974, which is a division of Ser. No. 250,] 19, May 4, 1972, Pat. No. 3,843,669,

[30] Foreign Application Priority Data May 7, 1971 United Kingdom 13723/71 [52] US. Cl. 424/270; 424/263; 424/272; 424/DIG. 8

[51] Int. Cl. AOlN 9/14;AO1N 9/22; AOlN 9/28 [58] Field of Search 424/263, 270, 272; 260/3067 [56] References Cited UNITED STATES PATENTS 3,681,479 8/1972 Gutman 260/04 Primary Examiner.lerome D. Goldberg Assistant Examiner-Allen J. Robinson Attorney, Agent, or FirmCushman, Darby & Cushman [57] ABSTRACT Compounds of the formula where R and R which may be the same or different, are hydrogen, alkyl containing up to four carbon atoms, phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl; and Y is oxygen, sulphur or alkylimino containing up to four carbon atoms; or (ii) Y is a group of the formula:

where R and R which may be the same or different, are hydrogen, alkyl containing up to four carbon atoms, phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl; and X is oxygen, sulphur or alkylimino containing up to four carbon atoms; useful as pesticides 2 Claims, No Drawings CARBAMOYLOXYIMINO-AZOLIDINES AS MOLLUSCICIDES This is a division of application Ser. No. 478,043, filed June 10, 1974, which is itself a divisional of Ser. No. 250,119, filed May 4, 1972, now US. Pat. No. 3,843,669.

This invention relates to new organic compounds and processes for preparing them, to compositions comprising them, and to methods of combating pests using them. More particularly this invention relates to new carbamoyloxime derivatives and processes for preparing them, to pesticidal compositions comprising them, and to methods of combating insect and other invertebrate pests using them.

Accordingly, the present invention provides compounds of formula:

wherein Q is oxygen or sulphur, or the sulphoxide or sulphone group; R, R and R, which may be the same or different, are hydrogen, or unsubstituted, or substituted, hydrocarbyl or heterocyclic radicals; and either (i) X is a group of formula:

where R and R which may be the same or different, are hydrogen, or unsubstituted, or substituted, hydrocarbyl radicals, or the acyl residues of carboxylic or sulphur-containing acids; and Y is oxygen, sulphur or the hydrocarbylimino radical; or (ii) Y is a group of formula:

where R and R, which may be the same or different, are hydrogen, or unsubstituted, or substituted, hydrocarbyl radicals, or the acyl residues of carboxylic or sulphur-containing acids; and X is oxygen, sulphur, or the hydrocarbylimino radical.

In one aspect the invention also provides compounds of formula:

wherein R, R and R are hydrogen atoms or unsubstituted, or substituted, hydrocarbyl groups; n has the value zero, one or two; and wherein either (i) X is a group of formula:

where R and R are hydrogen or hydrocarbyl groups, and Y is oxygen or sulphur or the hydrocarbylimino group; or (ii) Y is a group of the formula:

where R and R are hydrogen or hydrocarbyl groups, and X is oxygen or sulphur or the hydrocarbylimino group.

Preferred compounds are those provided by the invention of formula:

gen-containing aromatic monocyclic heterocycle; and either (i) X is a group of formula:

where R and R", which may be the same or different, are hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl; and Y is oxygen, sulphur or alkylimino; or (ii) Y is a group of formula:

where R and R, which may be the same or different, are hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl; and X is oxygen, sulphur or alkylimino.

In a more preferred aspect the invention provides compounds of formula:

3 4 R wherein R and R which may be the same or different, 0 are hydrogen, or alkyl containing up to four carbon R ll atoms; R is hydrogen, alkyl containing up to eight carbon atoms, allyl, benzyl, dimethylamino, methylthi- R 5 omethy], ethoxycarbonylmethyl, or halo-substituted R2 pyridyl; and R and R", which may be the same or different. are hydrogen, methyl, phenyl, chlorowherein Q is an oxygen or sulphur atom, or the sulph- Substituted phenyl acetyl chlfflomethyl memo)- 1 2 ymethyl, ethoxymethyl or ethylthiomethyl. oxide or sulphone group; R and R which may be the 1O Especially preferred compounds are those having the same or different are hydrogen or alkyl; R' hydrogen, f l alkyl. alkenyl, alkylthioalkyl, alkyl-substituted amino, Ormu aralkyl, ester-substituted alkyl, or a halo-substituted nitrogencontaining aromatic monocyclic heterocycle; 0 and R and R which may be the same or different, are l hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, 15 0 haloalkyl, alkoxyalkyl or alkylthioalkyl. u o

in an even more preferred aspect the invention pror/ vides compounds of formula:

N C o N= r/ wherein R' is alkyl contaimng up to four carbon atoms; R and R are hydrogen or alkyl containing up to four carbon atoms; R is hydrogen or methyl; and R is R. methyl.

Specific examples of compounds according to the wherein R and R'-, which may be the same or different formula: are hydrogen or alkyl; R" is hydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substituted amino, aralkyl, estersubstituted alkyl, or a halo-substituted nitrogencontaining aromatic monocyclic heterocycle; and R 5 Ru 0 and R which may be the same or different, are hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl. 4

In a even yet more preferred aspect the invention R provides compounds of formula: I R

R2 R %o are set out in Table I below, where the meanings of R, l R R, R and R are given together with a melting point (mp) each compound expressed in degrees cen- R tigrade.

TABLE I Compound No: R R2 R" R4 R5 m.p. C

1 H H CH,CH CH, CH, H 122 2 H H CH, CH, H 2l6 3 H H (,H, CH, H 218 4 3 1; H1 H 134.5 5 H H n C,H, CH, H us a H H n C,,H, CH, CH, 52 7 CH" CH3 CH5; CH3 CH3 8 CH, CH, H CH, H 240 9 H1. H H" H" H 13x 10 CH, CH, H, CH, H 107 l H H CH, CH, CH, 168 12 CH, CH( CH CH, H 97 1 3 CH, CH, H. .SCH, CH, H 106 14 H CH, CoCH, 161 I5 CH CH, CH. ,CH=( H CH, H 1e CH. ,CH CH, H CH, CH, H I30 17 C. .H,-, H CH, CH, H l 24 CH, CH, CH, CH, H 98 I9 CH(CH,). H CH, CH, H I20 In another aspect the invention provides compounds wherein R, R and R are alkyl groups containing up to four carbon atoms; R and R are hydrogen or alkyl containing up to four carbon atoms, and n has the value one 01' two.

Specific compounds according to the formula:

are set out in Table 2 below, where the meanings of R, R R, R and R are given, together with the value of n and a melting point for each compound.

In another aspect the invention provides compounds of formula:

Specific compounds according to the formula:

R ll

are set out in Table 3 below, where the meanings of Y, R, R R R and R are given together with a melting point for each compound.

TABLE 3 Compound No: R R R R" R" Y nip. (1

44 CH CH CH H CH S l 47 45 CH CH CH CH; CH S 2 l 8 46 CH CH; CH CH H NC ,H Oil In another aspect the invention provides compounds of formula:

wherein R, R and R are alkyl groups containing up to four carbon atoms; and R and R are hydrogen or alkyl groups containing up to four carbon atoms.

A further specific compound of the present invention is that having the formula:

(Compound N0. 47, mp. 135C) The invention compounds may be prepared by treating an oxime of formula:

Thus the invention provides a process for the preparation of compounds of the formula:

wherein R, R R and R have any of the meanings as defined hereinbefore and wherein R is hydrogen which comprises treating an oxime of formula:

with an isocyanate of formula:

R -N=C=O The invention also provides a process for the preparation of a compound of the formula:

wherein R, R R, R and R have any of the meanings as defined hereinbefore except that R" and R cannot be hydrogen, which comprises treating an oxime of formula:

HON=

with a carbamoylhalide of the formula:

wherein Hal is a halogen atom, for example, a chlorine or bromine atom.

The invention also provides a process for the preparation of a compound of formula:

9 wherein R, R R, R and R have any of the meanings as defined hereinbefore, which comprises treating an oxime of formula:

5 3 I HON Q l with phosgene and then bringing the product of such treatment into reaction with an amine of formula R*R"NH.

Such carbamoylation reactions are as outlined above are conveniently carried out in the presence of a base. Suitable bases include tertiary amines, for example triethylamine, or diethylaniline, aprotic nitrogen hetero cycles for example pyridine or N-methylmorpholine, and alkali metal carbonates for example potassium carbonate. The reactions may also be carried out in the may also be prepared by the treatment of a compound of formula:

with a halogen compound of formula R Hal, conveniently in the presence of a base, for example sodium hydride. Compounds of formula:

R 0 O l N c o N= RM 1 0 wherein R, R R, R and R have any of the meanings as defined hereinbefore and n has the value one or two may be prepared by the oxidation of a compound of formula:

with an oxidising agent, for example, hydrogen peroxide in the presence of an acid, for example acetic acid. Compounds of formula:

may be prepared by any of the carbamoylation procedures outlined above from an oxime of formula:

3 HON= IJ 1 Invention compounds of formula:

wherein R is an acyl group may be obtained by treating an invention compound of formula:

with an acylating agent, for example an acyl halide. where Y, R, R and R have any of the meanings as de- Invention compounds of formula: fined hereinbefore, may be treated with hydroxylamine to give the oxime of formula:

Y R4 I N J j NCON= R-/ HO wherein R" is a chloromethyl group may be obtained by treatment of a compound of formula: The thiones of formula:

R 0 o O k- R N H CO N= with formaldehyde and hydrogen chloride.

Such chloromethylated compounds may be subsemay be obtained by the well-known method of reacting quently reacted with alcohols and thiols to yield inventogether a compound of formula: tion compounds wherein R is alkoxyalkyl or alkylthioalkyl.

The oximes used as intermediates in the preparation S of the invention compounds may be obtained by treatment of the corresponding thiones with hydroxyl- B AH amines, thus for example a compound of formula:

R/ R l P (usually in the form of a metal or ammonium salt i 7 N thereof) with a haloacid of formula: or 1 R l 1 R R I 2 R Hal C COOH wherein R, R and R have any of the meanings as defined hereinoefore, may be treated with hydroxylamine R to yield an oxime of formula:

1 f where Hal is a halogen atom.

3 01" EM] An alternative method of preparing the oximes of formula: HO 1 HON S R O l Similarly a compound of formula: Ho

R 1 I Y particularly those wherein R is a hydrogen atom, in- R volves the treatment of an imine of formula:

with hydroxylamine. Such imines may be obtained by the reaction of a thiourea of formula:

i NH. )CNHR with a haloacid of formula:

Hal-(L-COOH The thiones of formula:

Where Y is sulphur may be obtained from the thiones of formula:

by treating the latter with phosphorus pentasulphidei If desired the thiones of formula:

may first be treated with an amine to yield a compound of formula:

where Y is hydrocarbylimino, before the treatment with phosphorus pentasulphide. I

The compounds of this invention or compositions as hereinafter defined may be used to combat a variety of insect and other invertebrate pests including the following:

(red spider mite) (black aphid) (mosquito) (green aphid) (white butterfly larva) (diamond back moth larva) (mustard beetle) Culundm gruliuria (grain beetle) 'I'rihnlium (m /1mm (flour beetle) Mm'ca dulnavll'tu (housefly) Blane/[u germunica (cockroach) Agriulimux reticulum/x (grcy field slug) Mz'loidngym' ilit'ognilu (nematodes) A particularly useful feature of the activity of the invention compounds is their ability to act as systemic pesticides, that is to say, their ability to move through a plant to combat infestations thereon at a site remote from the site of application of the compound.

The compounds and compositions of this invention may also be used to control a variety of plant pathogens including the following fungal diseases of plants:

(rust on wheat) (late blight on tomato) (downy mildew on vine) (powdery mildew on apple) (powdery mildew on vine) (blast on rice) (grey mould on vine) wherein Q is oxygen or sulphur, or the sulphoxide or sulphone group; R, R and R, which may be the same or different, are hydrogen, or unsubstituted, or substituted, hydrocarbyl or heterocyclic radicals; and either (i) X is a group of formula:

where R and R", which may be the same or different, are hydrogen, or unsubstituted or substituted, hydrocarbyl radicals, or the acyl residues of carboxylic or sulphur-containing acids; and Y is oxygen, sulphur, or the hydrocarbylimino radical; or (ii) Y is a group of formula:

where R and R, which may be the same or different, are hydrogen. or unsubstituted or substituted, hydrocarbyl radicals, or the acyl residues of carboxylic or sulphur-containing acids; and X is oxygen, sulphur, or the hydrocarbylimino radical.

in a preferred aspect the invention provides a pesticidal composition comprising as an active ingredient a compound of formula:

wherein Q is an oxygen or sulphur atom, or the sulphoxide or sulphonc group; R and R which may be the same or different are hydrogen or alkyl; R is hydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substituted amino, aralkyl, alkylthioalkyl, alkyl-substituted amino, aralkyl, ester-substituted alkyl, or a halosubstituted nitrogencontaining aromatic monocyclic heterocycle; and R and R which may be the same or different, are hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl.

In a more preferred aspect the invention provides a pesticidal composition comprising as an active ingredient a compound of formula:

wherein R and R which may be the same or different are hydrogen or alkyl; R is hydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substituted amino, aralkyl, estersubstituted alkyl, or a halo-substituted nitrogencontaining aromatic monocyclic heterocycle; and R and R", which may be the same or different, are hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl.

In an even more preferred aspect the invention provides a pesticidal composition comprising as an active ingredient a compound of formula:

wherein R is alkyl containing up to four carbon atoms; R and R are hydrogen or alkyl containing up to four carbon atoms; R is hydrogen or methyl; and R is methyl.

In an especially preferred aspect the invention provides a pesticidal composition comprising as an active ingredient the compound having the formula:

The compositions may be used for agricultural or horticultural purposes and the type of composition used in any instance will depend upon the particular purpose for which it is to be used.

The compositions may be in the form of dusting powders wherein the active ingredient is mixed with a solid diluent or carrier. Suitable solid diluents or carriers may be, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesium, Fullers earth, gypsum, Hewitts earth, diatomaceious earth and china clay.

The compositions may also be in the form of liquid preparations to be used as dips or sprays which are generally aqueous dispersion of emulsions containing the active ingredient in the presence of one or more wetting agents, dispersing agents, emulsifying agents or suspending agents.

Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anion or non-ionic type. Suitable agents of the cationic type include, for example quaternary ammonium compounds, for example, cetyltrimethylammonium bromide. Suitable agents of the anionic type include, for example, soaps, salts of aliphatic mono-esters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyland triisopropylnaphthalene sulphonic acids. Suitable agents of the non-ionic type include, for example; the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol or with alkylphenols such as octylphenol, nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are, for example, hydrophilic colloids, for example pol yvinylpyrrolidone and sodium carboxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth.

The aqueous dispersion or emulsions may be prepared by dissolving the active ingredient or ingredients in an organic solvent which may contain one or more wetting, dispersing or emulsifying agents and then adding the mixture so obtained to water which may likewise contain one or more wetting, dispersing or emulsifying agents. Suitable organic solvents are isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichloroethylene.

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane.

By the inclusion of suitable additives for example for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different composi tions can be better adapted for the various uses for which they are intended.

The compositions which are to be used in the form of aqueous dispersions or emulsions are generally sup plied in the form of a concentrate containing a high proportion of the active ingredient or ingredients, the said concentrates to be diluted with water before use. These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain -85 percent by weight of the active ingredient or ingredients.

When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient or ingredients depending upon the purpose for which they are to be used.

For agricultural or horticultural purposes, an aqueous preparation containing between 0.0001% and 0.1% by weight of the active ingredient or ingredients may be used.

The compositions of the present invention may, if desired, also comprise in addition to a compound of the present invention, at least one other biologically active ingredient. for example, in insecticide, or a fungicide.

Thus, for example, a composition of the present invention may comprise a compound of the present invention together with the gamma isomer of l.2,3.4,5,6- hexachlorocyclohexane.

In use. the invention compounds of compositions may be used to combat pests in a variety of ways. Thus the pests themselves, or the locus of the pests or the pest habitat may be treated to control the pests.

in a further feature therefore the invention provides a method of combating pests wherein the pests, the locus of the pests, or the habitat of the pests is treated with a compound or a composition according to the invention.

The invention also provides a method of treating plants with a compound of composition according to the invention to render them less susceptible to damage by pests, which may already be occurring (i.e. treatment to eradicate an infestation or infection) or which is expected to occur (i.e. treatment to protect the plant from an infestation or infection).

In a yet further feature, therefore, the invention provides a method of treating plants to render them less susceptible to damage by pests, which comprises treating the plants, or the seeds, corms, bulbs, tubers, rhizomes or other propagative pans of the plants, with a compound or composition according to the invention.

If desired the medium in which the plants are growing may be similarly treated with a compound or composition according to the invention.

In another feature, therefore the invention provides a method of treating a medium in which plants are growing or to be grown which comprises applying to the medium a compound or composition according to the invention.

The invention is illustrated, but not limited, by the following examples.

EXAMPLE 1 This example illustrates the preparation of 3,5,5- trimethyl thiazolidin-4-one-2-thione having the formula:

To a solution of methylamine in ethanol (33% w/v, 20 ml.) was added (40 ml.) and the mixture was cooled to 0C, whilst carbon disulphide (7.6 g) in ethanol (l0 ml.) was added with stirring over a period of 5 minutes. After stirring for a further 15 minutes ethyl 2-bromoisobutyrate (19.4 g) was added over 5 minutes after which the mixture was refluxed for 3 hours. The mixture was then cooled and kept at the ambient temperature for 18 hours. After removal of the ethanol by evaporation under reduced pressure the residual solid was treated with water ml), collected by filtration, washed with water and recrystallised from aqueous ethanol to give 3,5,S-trimethylthiazolidin-4-one-2-thione, melting at 96C.

EXAMPLE 2 Compounds of formula:

R3 l N wherein R, R and R have the meanings given in the Table below were prepared by a similar method to that illustrated in Example 1 using the appropriate reactants in each case. A physical characteristic is given for each compound.

This example illustrates the preparation of 5,5- dimethyl-2-imino-thiozolidin-4-one, having the formula:

H I N 1% C CH EXAMPLE 4 By asimilar method to that illustrated in Example 3 the following compounds were also prepared:

2-iminothiazolidin-4-one, melting at 258C;

5-ethyl-2-iminothiazolidin-4-one, melting at 200C;

and

5-iso-propyl-2-iminothiazolidin 4-one,

melting at EXAMPLE 5 This example illustrates the preparation of 2- oximino-B, 5.5-trimethylthiazolidin-4-one, having the formula:

H p/O now= 3,5.5-Trimethylthiazolidin-4-one-2-thione (62.0 g), hydroxylamine hydrochloride (75.0 g). pyridine (75.0 ml) and ethanol (750 ml) were refluxed together for 8 hours. The mixture was cooled and diluted with water. The precipitate was collected by filtration and recrystallised from a mixture of benzene and petroleum ether to yield 2-oximino-3,5,5-trimethyl-thiazolidin-4-one having a melting point of 216C.

EXAMPLE 6 By a procedure similar to that illustrated in the preceeding example compounds of formula:

wherein the values of R, R and R are those set out in the following table, were also prepared. The table also includes a melting point in degrees Centigrade for each compound.

R R R" m.p. "C H H CH. 22 H H C. .H 218 H H n c,.H 162 (2H5 C2H,-, H 166 CH1, CH1 N( CH 174 CH. C H CH 180 EXAMPLE 7 This example illustrates the preparation of 2- oximino-5,5-dimethyl-thiazolidin-4-one having the structure:

5,S-dimethylthiazolidin-2-imino-4-one (8.3 g), hydroxylamine hydrochloride (200g), pyridine (25.0 ml) and ethanol ml) were mixed and refluxed for 2.5 hours, and kept at room temperature for 16 hours, after which the volatiles were removed under reduced pressure and the residue treated with water. The precipitate was collected by filtration and recrystallised from ethanol to give 2-oximino-5.5-dimetl:ylthiazolidin-2-one, having the melting point of 204C.

EXAMPLE 8 By the use of a procedure similar to that illustrated in the preceeding example the following compounds were also prepared. They all conform to the formula:

and the values for R, R and R together with a melting point in degrees Centigrade are set out in the table below.

This example illustrates the preparation of 3,5,5- trimethyl-2-methyl-carbamoyloxyiminothiazolidin- 4-one, (Compound No. 4, Table I) having the formula:

2-Oximino -3,5,5-trimethylthiazolidin-4-one (15.0 g) was suspended in chloroform and methyl isocyanate (5.0 g) added, together with triethylamine (4 drops). After keeping for 4 hours at room temperature the solvent was evaporated at reduced pressure and the residual solid recrystallised from benzene to yield 3,5,5- trimethyl-Lmethylcarbarnoyloxyiminothiazolidin- 4-one, having a melting point of l34.5C.

EXAMPLE A similar procedure to that illustrated in the preceeding example was used for the preparation of the following compounds, using the appropriate intermediate oxime as follows:

3-isopropyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.1. Table I) from 3-isopropyl- 2-oximinothiazolidin-4-one;

methyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.2, Table I) from 3-methyl-2- oximinothiazolidin-4-one; 3-ethyl-2-methylcarbarnoyloxyiminothiazolidin-4-one (Compound No.3, Table I) from 3-ethyl-2- oximinothiazolidin-4-one; 3-n-octyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.5, Table I) from 3-n-octyl-2- oximinothiazolidin-4-one;

3,S-dimethyl-Z-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.9, Table I) from 3,5-dimethyl- 2-oximinothiazolidin-4-one; 3-dimethylamino-5,5-dimethyl-Z-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.23. Table I) from 3dimethylamino-5.5-dimethyl-2- oximinothiazolidin4-one; and 3,5-dimethyl-3-ethyl 2-methylcarbamoyloxyiminothiaZolidin-4-one (Compound No. 32, Table I) from 3,5-dimethyl-3-ethyl-2-oximinothiazolidin-4-one.

EXAMPLE 1 I This example illustrates the preparation of 5,5- dimethyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.8, Table I) having the formula:

0 H ICI) CH,,NH C Q N=G 2-Oximino-5,5-dimethylthiazolidin4-one (4.0 g), chloroform ml), methyl isocyanate (2.0 ml) and triethylamine (3 drops) were mixed and kept at room temperature for 4 hours, after which the solvent was removed under reduced pressure. The residual solid was 5,5-dimethyI-Z-methylcarbamoyloxyminothiazolidin-4-one, melting at 240C.

EXAMPLE 12 A similar procedure to that illustrated in the preceeding example was used to prepare the following compounds, using the appropriate oxime as follows:

EXAMPLE [3 This example illustrates the preparation of 3-n-octyl- 2-dimethylcarbamoyloxyiminothiazolidin-4-one (Compound No.6, Table I), having the formula:

2-oximino-3-n-octylthiazolidin-4-one (4.5 g) was suspended in dry benzene 150 ml) and sodium hydride 1.0g of 50 percent dispersion in mineral oil) added in small portions at room temperature. After the initial effervescence had ceased the mixture was refluxed for 30 minutes and then cooled. Dimethylearbamoyl chloride (2.2 g) was then added and the mixture again refluxed for 60 minutes, after which the mixture was cooled, poured into water, the benzene layer separated, washed with water, and dried over anhydrous magnesium sulphate. After filtration the filtrate was evaporated under reduced pressure and the residual solid recrystallised from petroleum ether to yield 3-n-octyl-2- dimethylcarbamoyloxyiminothiazolidin-4-one having a melting point of 52C.

EXAMPLE 14 By a procedure similar to that illustrated in the preceeding example the following compounds were also prepared from the appropriate oximes:

3,5,5-trimethyl-2-dimethylcarbamoyloxyiminothiazolidin-4-one (Compound No.7, Table I) from 3,3,5- trimethyl-2-oximinothiazolidin-4-one; and

3-methyl-Z-dimethylcarbamoyloxyiminothiazolidin- 4-one (Compound No.l I, Table I) from 3-methyl-2- oximinothiazolidin-4-one.

EXAMPLE 15 This example illustrates the preparation of 3,3,5- trimethyl-Z-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.4, Table I) having the formula:

Sodium hydride (0.05 g) was added to 5,5-dimethyl- 2-methylcarbamoyloxyiminothiaZolidin-4-one (Compound No.8, Table I; 0.49 g) in dimethylformamide (25 ml). Hydrogen was evolved over a period of about 5 minutes after which the mixture was gently warmed for minutes. Methyl iodide (2 c.c.) was added and the mixture gently warmed for a further minutes, after which it was cooled, poured into water and extracted with chloroform. The chloroform extract was washed with water and dried over anhydrous magnesium sulphate. After filtration the filtrate was evaporated at reduced pressure and the resultant oil triturated with nhexane to yield 3,5,5-trimethyl-2-methylcarbamoyloxyiminothiaZolidin-4-one, identical with the product obtained by the method of Example 9.

EXAMPLE 16 By a procedure similar to that illustrated in the proceeding example there were prepared other invention compounds from the appropriate reactants as follows:

3-ethyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 10, Table I) from 24 5,5-dimethyl-Z-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.8. Table I) and ethyl iodide;

3-iso-propyl-5.5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4one (Compound No. l 2, Table I) from 5.5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.8, Table I) and isopropylbromide;

3-methylthiomethyl-5,5-dimethyl-2- methylcarbamoyloxyiminothiazolidin-4one (Compound No.l3, Table I) from 5,5-dimethyl-2- methylcarbamoyloxyiminotrhiaZolidin-4-one (Compound No.8, Table I and methyl chloromethyl thioether;

3-allyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.15, Table I) from 5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.8, Table I) and allyl bromide;

3-methyl-5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin4- one (Compound No.16, Table I) from 5iso-propyl 2-methylcarbamoyloxyiminothiazolidin- 4-one, (Compound No.38, Table l) and methyl iodide; 3-methyl-5-ethyl-2-methylcarbanoyloxyiminothiazolidin-4-one (Compound No.17, Table I) from S-ethyl- 2-methylcarbamoyloxyiminothiazolidin-4one (Compound No.40, Table I) and methyl iodide; 3-methyl-5-iso-propyl-Z-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.19, Table I) from 5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 39, Table I) and methyl iodide; 3-ethyl-5-iso-butyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 21, Table I) from 5-iso-butyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No.38, Table I) and ethyl iodide;

3-methyl-5,5-diethyl-2-methylearbamoyloxyiminothiazolidin-4-one (Compound No.22, Table I) from 5,5-diethyl-2-methyl carbamoloxyiminothiazolidin- 4-one (Compound No. 20, Table I) and methyl iodide;

3-ethyl-5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.24, Table I) from 5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 39, Table I) and ethyl iodide; 3-methyl-5-n-butyl-5-ethyl-2methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 26, Table I) from S-n-butyl-S-ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 25, Table I) and methyl iodide; 3-benzyl-5,5-dimethyl-2-methylearbamoyloxyiminothiazolidin-4-one (Compound No. 29, Table I) from 5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No.8, Table I) and benzyl chloride; 3-iso-butyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 30, Table I) from 5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 8, Table I) and iso-butyl bromide; 3-ethoxyearbonylmethyl-5,5dimethyl-2- methylcarbamoyloxyiminothiazolidin-4one pound No. 31, Table I) methylearbamoyloxyiminothiazolidin-4-one pound No.8 Table l) and ethyl chloroacetate;

(Comfrom 5,5-dimethyl-2- (Com- 3( 2,5-dichloro-2,6-difluoropyrid-4-yl )-5 ,5-dimethyl2- methylcarbamoyloxyiminothiazolidin-4-one C ompound No.41 Table 1) from 5.5-dimethyl-2- methylcarbamoyloxyiminothiaZolidin4-one (Compound No. 8 Table l) and 3,5-dichloro-2,4,6- trifluoropyridine; and

3-pivaloylmethyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 42, Table I) from 5,5-dimethyl-2-methylcarbamoyloxyimino thiazolidin-4one (Compound No.8 Table l) and chloromethyl t-butyl ketone.

EXAMPLE 17 This example illustrates the preparation 3,5,5- trimethyl-2(Nchloromethyl-N- methylcarbamoyl)oxyiminothiazolidin-4- one (Compound No. 33, Table I) having the formula:

ClCl-lx EXAMPLE 18 This example illustrates the preparation of 3,5,5- trimethyl-Z N-ethylthiomethyl-N- methylcarbamoyl)oxyiminothiazolidin-4-one pound No. 34 Table I) having the formula:

(Com- Ethane thiol (0.62 g) was added to a solution of sodium (0.23 g) in ethanol (25.0 ml) and to the stirred mixture was added a solution of 3,5.5-trimethyl-2(N- chloromethyLN-methylcarbamoyl )oxyiminothiazolidin-4-one (2.7 g.) in ethanol (25.0 ml) at the ambient temperature. After keeping at the ambient temperature for 18 hours the volatile components were removed by evaporation under reduced pressure. The residue was treated with water 100 ml.) and extracted with chloroform (2 X 25 ml.) The extracts were combined, dried over anhydrous magnesium sulphate. and evaporated to yield a solid which was recrystallised from petroleum ether (boiling range 6080C to yield 3 ,5 5-trimethyl2( N-ethylthiomethyl-N- methylcarbamoyl)oxyiminothiazolidin-4-one having a melting point of 74C.

EXAMPLE 19 This example illustrates the preparation of 3,5,5 trimethyl-2(N-methoxymethyl-N- methylcarbamoyl )oxyiminothiazolidin-4-one pound No. 35, Table 1), having the formula:

(Com- 3.3,5-trimethyl-2-(Nchloromethyl-N- methylcarbamoyl )oxyiminothiazolidin-4-one (2.0 g) was dissolved in methyl alcohol (50 ml.) warmed to 50C for a few minutes and then kept at the ambient temperature for 18 hours. Upon cooling to 0C a crystalline precipitate formed and this was collected by filtration and recrystallised from methanol to yield 3,3,5- trimethyl-2-( N-methoxymethyl-N-methylcarbamoyl oxyiminothiazolidin-4-one, melting at 1 16C.

EXAMPLE 20 By a procedure similar to that illustrated in the previous example the preparation of another invention compound was effected using the appropriate reactants as follows:

3 ,5 ,5-trimethyl-2( N-ethoxymethyl-N- methylcarbamoyl )oxyiminothiazolidin-4-0ne (Compound No. 36, Table 1) from 3.5,5,-trimethyl-2(N- chloromethyl-N-methylcarbamoyl )oxyiminothiazolidin-4-one (Compound No. 22, Table l) and ethyl alcohol.

EXAMPLE 21 This example illustrates the preparation of 3.35- trimethyl-2-phenylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 18, Table 1,) having the formula:

To a solution of 3,5,5trimethyl-2- oximinothiacolidin-4-one (2.6 g) in chloroform (50 ml.) was added phenylisocyanate (1.8 g) and triethylamine (2 drops). The mixture was kept at the ambient temperature for 18 hours, after which the volatile components were removed by evaporation under reduced pressure and the residual solid recrystallised from diethyl ether to yield 3,5,5-trimethy1-2- phenylcarbamoyloxyminothiazolidin-4-one, melting point at 98C.

EXAMPLE 22 By a similar procedure to that illustrated in the preceeding example the following compounds were also prepared using the appropriate reactants as follows: 3-methyl-2-phenylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 28, Table 1) from 3-methyl-2- oximinothiazolidin-4-one and phenyl isocyanate; and 3,5,5-trimethyl-2(3,4-dichlorophenyl)carbamoyloxyiminothiazolidin-4-one (Compound No. 37, Table I) from 3,5,5-trimethy1-2-oximinothiazolidin-4-one and 3,4-dichlorophenyl isocyanate.

EXAMPLE 23 This example illustrates the preparation of 3,5,5- trimethy1-2-carbamoyloxyiminothiazolidin-4-one (Compound No. 27, Table I) having the formula:

To a solution of 3,5,5-trimethy12-oximinothiazolidin- 4-one (5.0 g) in chloroform (200 ml.) was added a solution of phosgene (3.0 g) in toluene (30 ml). After stirring for one hour at the ambient temperature, the mixture was cooled to C and gaseous ammonia passed in for minutes. The solvents were removed by evaporation under reduced pressure and the residual solid recrystallised from a mixture of toluene and petroleum ether (boiling range 6080C) to yield a solid which did not melt, but sublimed at a temperature above 300C.

EXAMPLE 24 This example illustrates the preparation of 5,5- dimethyl-2-(N-acety1-N-methylcarbamoyl)oxyiminothiazolidin-4-one (Compound No. 14, Table I), having the formula:

EXAMPLE 25 This example illustrates the preparation of 3,5,5- trimethylthiazolidin-Z,4-dithione having the formula:

on s

A mixture of 3,5,S-trimethylthiazolidin-2-one-4-thione (8.7 g), phosphorus pentasulphide (6.0 g) and dioxan (150 ml) was refluxed with stirring for 4 hours, after which the mixture was kept at the ambient temperature for 18 hours. The liquid was decanted, the solid residue washed with hot dioxan (2 X 25 ml) and the washings combined with the decanted liquid and heated with animal charcoal (5.0 g) and zinc dust (6.0 g) for 10 minutes. The mixture was filtered whilst hot, and the solvent evaporated under reduced pressure to yield a residual solid, which was recrystallised from ethanol to yield 3,5,S-trimethylthiazolidin-2,4-dithione, melting at C.

EXAMPLE 26 This example illustrates the preparation of 3,5,5- trimethyl-4-oximino-thiazo1idin-2-thione having the formula:

if HON A mixture of 3,5,5-trimethylthiazolidin-2,4-dithione (6.0 g), hydroxylamine hydrochloride (11.0 g), pyridine 12.0 ml) and ethanol ml.) was refluxed for eight hours. Ethanol was evaporated under reduced pressure and water (200 ml.) added to the residue. The mixture was extracted with chloroform (3 X 50 m1.),

the combined chloroform extracts being washed with a w/v solution of hydrochloric acid (3 X 100 ml.) and with water 100 ml. dried over anhydrous magnesium sulphate, and evaporated under reduced pressure to yield a residual solid. This was recrystallised from petroleum ether (boiling range 80100C) to yield 3,5,5- trimethyl'4-oximinothiazolidin-2-thione, having a melting point of 142C.

EXAMPLE 27 This example illustrates the preparation of 3,5,5- trimethyl-Z-n-butyl-iminothiazolidin-4-on4 having the formula:

l c n m) A mixture of 3,5,5-trimethylthiazolidin-4-one-2-thione (57.8 g) n-butylamine (25.0 g) and ethanol (200 ml.) was refluxed for eight hours, after which time the ethanol and excess n-butylamine were removed by evaporation under reduced pressure. The residual oil was distilled to yield 3,5,5-trimethyl-2-nbutyliminothiazolidin-4-one, boiling at 90C/O.l6 mm. Hg, having 11,, 1.5079.

EXAMPLE 28 This example illustrates the preparation of 3,5,5- trimethyl-2-n-butyliminothiazolidin-4-thione having the formula:

C l-1 m) S:

f vH 3 A mixture of 3 ,5 ,5-trimethyl-2-nbutyliminothiazolidin-4-one (42.8 g) phosphorus pentasulphide (17.8 g) and dioxan (200 ml.) was refluxed for eight hours with brisk stirring after which the liquid was decanted, heated with animal charcoa1'(2.0 g.)'for 10 minutes, filtered whilst hot, and then evaporated under reduced pressure. The residual oil was distilled to yield 3,5,5-trimethyl-2-n-butylimonothiazolidin-4- thione, having a. boiling point of 10l1 ()2C/O.22

mm.Hg. v

I EXAMPLE 29 This example illustrates the preparation of 3,55- trimethyl-Z-n-butylimino-4-oximinothiazolidine having the formula:

3 1 nc n m) A mixture of 3,5,S-trimethyl-Z-n-butyliminothiazolidin-4-thione (18.6 g) hydroxylamine hydrochloride EXAMPLE 30 This example illustrates the preparation of 3,5,5- trimethyl-4-methyl-carbamoyloxyiminothiazolidin-Z- thione (Compound No. 44, Table 3) having the formula:

To a solution of 3,5,5-trimethyl-4-oximinothiazolidin-2-thione (5.7 g) in chloroform ml.) was added methyl isocyanate (2.1 g) and triethylamine (3 drops). The mixture was kept at the ambient temperature for 6 hours, after which the volatile components were removed by evaporation at reduced pressure, and the residual solid recrystallised from toluene to yield 3,5,5- trimethyl-4-methylcarbamoyloxyiminothiazolidin-Z- thione, melting at 147C.

EXAMPLE 3 l This example illustrates the preparation of 3,5,5- trimethyl-2-n-butylimino-4-methylcarbamoyloxyiminothiazolidine (Compound No. 46, Table 3) having the formula:

To a solution of 3,5,S-trimethyl-2-n-butylimino-4- oximinothiazolidine (2.6 g) in chloroform (50 ml.) was added methyl isocyanate 3.0 ml.) atthe ambient temperature, and the mixture was kept at this temperature for 18 hours. Evaporation of the volatile portion under reduced pressure yielded a viscous oil which was identifled by infra-red and n.m.r. spectroscopy as 3.5.5 trimethyl-2-n-butylimino-4-methylcarbamoyloxyiminothiazolidine.

EXAMPLE 32 This example illustrates the preparation of 3,3,5- trimethyl-4-dimethylcarbamoyloxyiminothiazolidin-2- thione (Compound No. 45, Table 1) having the for mula:

A mixture of 3,5,5-trimethyl-4-oximinothia2olidin-2- thione (2.6 g), chloroform (30 ml.), pyridine ml.) and dimethylcarbamoyl chloride (2.0 ml.) was refluxed for 90 minutes, after which the volatile components were removed by evaporation under reduced pressure. The residue was treated with water, collected by filtration, and recrystallised from ethanol to yield 3,5,5- trimethyl-4-dimethylcarbamoyloxyiminothiazolidin-2- thione. melting at 218C.

EXAMPLE 33 This example illustrates the preparation of the compound 3,5,5-trimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one 1,1-dioxide (Compound No. 43, Table 1) having the formula:

l 0 0 CH,,

To a mixture of 3,5,5-trimethyl-2- methylcarbarmoyloxyiminothiazolidin-4-one (4.6 g) and glacial acetic (25.0 ml.) was added, at the ambient temperature, hydrogen peroxide solution (30 volume,

EXAMPLE 34 This example illustrates the preparation of 2- oximino-3,5,5-trimethyloxazolidin-4-one having the formula:

HON

A mixture of 3,5,5-trimethyloxazolidin-4-one-2-thione (15.0 g) hydroxylamine hydrochloride (25.0 g) pyridine (27.0 g) and ethanol (200 ml.) was refluxed for four hours, after which the volatile portion was removed by evaporation under reduced pressure. The residual oil was poured into water (200 ml.) and the solid which precipitated out was collected by filtration, washed with water and dried to yield 2-oximino-3,5,5- trimethyl-oxazolidin-4-one, having a melting point of 246C.

EXAMPLE 35 This example illustrates the preparation of 3,5,5- trimethyl-2-methylcarbamoyloxyiminooxaxolidin- 4-one (Compound No. 47) having the formula:

A mixture of 2-oximino-3,5,S-trimethyloxazolidin- 4-one (5.9 g) chloroform ml) and methyl isocyanate (2.2 g) was kept in a moisture free atmosphere at the ambient temperature for 18 hours. Evaporation of the volatile portion of the mixture under reduced pressure yielded (3,5,S-trimethyl-2-methyl-carbamoyloxyimino-oxazolidin-4-one, Melting at C.

EXAMPLE 36 The activity of a number of the compounds was .tested against a variety of insect and other invertebrate pests. The compounds were used in the form of a liquid preparation containing 0.1% by weight of the compound except in the tests with Aedes aegypli where the preparations contained 0.01% by weight of the compound. The preparations were made by dissolving each of the compounds in a mixture of solvents consisting of 4 parts by volume of acetone and 1 part by volume of diacetone alcohol. The solutions were then diluted with water containing 0.01% by weight of a wetting agent sold under the trade name LISSAPOL" NX until the liquid preparations contained the required concentration of the compound. Lissapol is a Trade Mark.

Thetest procedure adopted with regard to each pests was basically the same and comprised supporting a number of the pests on a medium which was usually a host plant or a foodstuff on which the pests feed, and treating either or both the pests and the medium with the preparations.

The mortality of the pests was then assessed at periods usually varying from one to three days after the treatment.

33 34 The results of the tests are given below in Table 4. In sessment is expressed in integers which range from O-3. this table the first column indicates the name of the represents less than 30 percent kill pest species. Each of the subsequent columns indicates 1 represents 30-49 percent kill the host plant or medium on which it was supported, 2 represents 5090 percent kill the number of days which were allowed to elapse after 3 represents over 90 percent kill the treatment before assessing the mortality of the A dash in Table 4 indicates that no test was carried P and the Tfislllts Obtamed for each of th C out. The symbol A indicates that an antifeeding effect pounds, numbered as 1n Tables 1 to 3 above. The aswas observed.

TABLE 4 Pest Species Support No of COMPOUND NO:

Medium days 1 2 4 6 8 9 l() ll l2 l3 l5 l7 I9 22 23 4 I'ulrunyclmxlcluriux French 3 U U 3 3 2 3 3 3 3 t) (l U 2 3 3 l (red spider mites. adults Bean lZ'Ilun \'(/IH.\' Ielm'im' French 3 t) (l U l 0 U 3 (J 2 (l 0 3 U 2 (red spider mites. eggs) Bean sip/11's fulmc Broad 2 (1 3 (l (l 3 3 3 3 3 3 3 U 3 3 3 (green aphids) Bean Muguum Vic-um Broad 2 l) 3 t) (l 3 3 3 3 (l 3 3 l 3 3 (black aphids) Bean Anlmutqe tpli Water l 3 (J 3 0 2 (l l l) U U U 0 3 O (J (mosquito larvae) .it'llt'X tlt' q \'/)li Plywood l l (l O l) 2 (l O I (l (l (l' (l O I 2 l) (mosquito adults) NIHSLU(IUIHLJIILYI Milk/ 2 2 Z (J l O 3 (l (l 2 l) 2 2 l l) (houseflies-contact test*) Sugar Mum-utlnnucxlim Plywood 2 O U t) I l) (l (l (I (l U U (housefliesmesidual tcst* lilaln'llugcrnmnica I O l) 2 U l t) 3 (J "4 3 (coehroaches) Pest Species Support No: of COMPOUND NO:

Medium days I 2 4 5 7 9 ll) ll l2 l5 l7 I8 I9 20 2l 22 23 Pit-Fix lu'uxxit'ur' Cabbage 2 3 U 2 3 3 3 3 2 U 3 2 (l 3 3 (cabbage white caterpillars-systemic A A A A A A A A A A A A (CS!) Picrix ln'uxxit'm' Cabbage 2 0 l) 3 (I (J (l 3 3 (I U 3 U (I (l 3 3 (cabbage white caterpillars A A A A A A (Contact test) PIHlU/[llIHtltllipl'lllliS Mustard 2 l) O 2 t) l) l) 2 l) (l l) (l (I (diamond back moth. A A A larvae systemic test) PIN/('11:!HllILlI/ipt'lllliX Mustard 2 (l l) U U U U 0 (l 0 (t (l 0 (diamond back moth- A A A A larvae contact test) P/IzR'tIOH(0('/I]('Ul'illl' Mustard 2 O 2 3 t) 3 1 3 2 2 3 U 2 U (I 3 2 (mustard beetles residual test) P/Hltt/UII('(lt'llt'lll'itlt Mustard 2 3 O 0 t) (mustard beetles A A systemic test) (ulumlm grulml'iu Grain 2 (l i) (J (l O 2 U 0 O O (I 0 l (l 2 0 (grain beetles) 'l'rilmlimn(m /mum Grain 2 0 U U 0 t) l) t) O U 0 t) 2 (flour beetles) Mvluidugynt'ilimgnim Water I 0 l) (l 'l t) 3 l) 0 t) O 3 3 3 l) (nematodes) Pest Species Support No. of COMPOUND NO:

Medium days 26 29 30 3] 32 33 35 36 43 43A 44 46 47 'll'lrunyvlmx lvlurim French 3 0 0 l) 0 3 3 0 U 0 0 l 2 (red spider mites. adults) Bean 'll'lrulrrclmx Icluriux French 3 0 (l 0 O 2 U U O O U U (I 0 (red spider mites. eggs) Bean AplnIs-firlmc Broad 2 l) 0 3 3 3 (I l) O 3 U 3 (green aphids) Bean Meguuru ritmt' Broad 2 O 0 O 3 3 3 (l 0 (I 3 U 3 (black aphids) Bean Aer/0x uqrgypti Water I (J 0 O 3 3 l (J 3 3 (mosquito larvae) Anita near Hi Plywood l (l 2 2 l) 0 O l) (J U 2 (mosquitos adults) ll/fm't'uzlumcxliul Milk/ 2 2 l) l (l 2 U 0 O 2 l 3 (houseflies-eontaet test*) Sugar i'VIm't'uzlnmt'slicu Plywood 2 (l 0 0 O 0 O l) U 0 (housefliesmesidual test* Blane/[ugtrlmmicu l 0 (l (l O 3 3 2 l) 0 O O U 3 (eochroaches) Pest Species Support No. of COMPOUND NO;

Medium days 24 26 29 3() 31 32 33 35 4| 43 44 45 46 47 Pierix brusxiz'm' Cabbage 2 0 3 O O 2 3 0 3 (cabbage white cater- A A A pillars temie test) Pit'rix hrussiz'ue' Cabbage Z Z 3 3 l) 2 2 O O 3 (cabbage white cater pillars contact test) A A A A A TABLE-4 Continued Pest Species Support No. of COMPOUND NO:

Medium days 1 2 4 6 x 9 1o 11 l2 I3 15 I7 I) 22 23 24 IIulellu lmlt'llli x'l nix Mustard 2 (l (l (l 0 0 0 (l 0 (l 0 3 0 (diamond hack moth. A A A larvae systemic test) P/mulla mm'uli x'nniv Mustard 2 0 (l 0 0 (l 0 0 0 0 0 0 2 (diamond hack moth. A A larvaecontact test) llmczlmi (och/curiae Mustard 2 l l) 0 0 0 3 3 0 0 0 0 I 3 (mustard beetles residual test) A A A A A A A A A P/mulun ouch/curiae Mustard 2 t) (l U 3 (l 0 0 0 3 3 (mustard beetles systemic test) A A A A A ('uIu/ulm unumriu (jrain 2 0 I) 0 0 2 0 0 (l 0 0 0 0 1 (grain beetles) 'Iri/mlinm (m /inn"! Grain 2 U (l (l (l (l I (l (l 0 (l O 0 (flour beetles) Mcluiilugym' inmgni/u Water 1 0 0 3 0 3 (l 0 3 2 3 2 (nematodes) In the Contact test the flies are sprayed directly; in the residual tcst nique employed is to spray the foliage of the undiseased the flies are placed on a medium that had previously been treated. ln the systemic tests the preparations are applied to the soil in which the plants wlth a i of the test compound and a to host plants are growing. drench the $01] in whlch the plants are growing with another solution of the same test compound. All solutions 25 EXAMPLE 37 for spraying and drenching contained 0.01 percent of the test compound. The plants were then infected with Compounds of the "Wemlon were tested for mollus the diseases it was desired to control and after a period cicidal activity and details of the tests conducted are as of days, depending upon the particular disease, the follows' tent of the disease was visually assessed. The results are d i c l o g f thehcomlpougd under tes t was given in Table 6A below, wherein the extent of the dislsso ve m cc 0 et an a mxture ease is given in the form of a grading as follows: (50:50 v/v). The solution was diluted with 0.5 cc. water and poured on to a calf feeding pellet in a glass petri dish and the pellet was air dried for 24 hours. The x5 weight of compound used chosen so tha t the dried Grading Percentage Anmum of Disease pellet contained 4% by weight of the active ingredient. 0 61 m 100 Two replicates each consisting of a plastic petri dish l 2? O containing a pellet, 2 slugs, and a moistened filter paper 3 0 m 5 to maintain a high relative humidity were used in each 40 test. The dishes were left in the cold room 10C). After 6 days the kill was assessed.

The slu s used were A riolimax reticulatus Mull g g In Table 6 the disease IS given in the first column, and and they had been starved for 24 hours before the com- 1n the second column is given the time which elapsed mencement of the tests. The results of the test are set between infecting the plants and assessing the amount out in Table 5 below.

of disease.

TABLE 5 Compound No. 72 kill Compound N0: 7r kill TABLE 6 I 50 20 mo Disease and Plant Time intcr- Disease Code 7 100 2] 50 'l D' L n r (T bl 6A) 9 100 22 100 c c 10 100 23 100 I 12 50 26 I00 Pucz'mm IL'L'()I|(Iifl| 7 A 15 100 32 100 (Wham) 16 I00 33 50 P/IylnpIzI/mru Ir /exmlm' 3 B 17 50 35 100 (0mm I 19 5O 47 m0 Plasmoparu vmcolu 7 C (vine) Um'inulu nec'amr l0 D (vine) Piliculuria uryzue 7 E (rice) EXAMPLE 38 Puduxp/zuera leuz'ulriclm 10 F (apple) The compounds of this invention were tested against 'i 3 G 5 VlnC a variety of foliar fungal diseases of plants. The tech- -Continued TABLE 6A Compound No: Disease Code Letter A B C D E F G 6 0 O (l 3 0 9 3 l 2 3 0 l l5 0 l 3 3 O 0 0 l6 l 3 0 O 0 l7 3 3 3 3 O 0 0 l8 0 0 0 0 O 2 2O 0 3 3 l 2 O 21 0 2 3 -0 0 U- 22 ,l 3 O O V l .0 24 0 3 O 3 l 2 26 0 3 0 O l 0 I l 3O 0 3 0 l g 0 v 0 0 31 O 0 0 0 0 2 0 32 (l 3 0 "l l 0 33 l 3 0 l 0 1 v3 34 l I 0 0 l l 35 2 l 0 0 0 43 l 2 0 0 3 44 0 4 3 3 l 0 l 45 U 3 0 l (J 0 EXAMPLE 39 This example illustrates a dusting powder which may be applied directly to plants or other surfaces and comprises 1 percent by weight of compound No. 40f Table l and 99 percent by weight of talc.

EXAMPLE 40 EXAMPLE 41 5 Parts by weight of Compound No. 4 of Table I were thoroughly mixed in a suitable mixer with 95 Parts by weight of talc. There was thus obtained a dusting powder.

EXAMPLE 42 Parts by weight of Compound No. 4 of Table I, 10 parts of an ethylene oxideoethylphenol condensate (Lissapol NX: Lissapol is a Trade Mark) and 80 parts by weight of diacetone alcohol were thoroughly mixed. There was thus obtained a concentrate which, in mixing with water, gave an aqueous dispersion suitable for application as a spray in the control of insect pests.

EXAMPLE 43 This example illustrates a concentrated liquid formulation in the form of an emulsion. The ingredients listed below were mixed together in the stated proportions and the whole stirred until the constituents were dispersed.

7: wt. Compound No 4 of Table l LUBROL [.(Lubrol is a Trade Mark) 17 Calcium dodecylbenzcnesulphonate 3 Ethylene dichloride 45 AROMASOL H(Aromasol is a Trade Mark) EXAMPLE 44 The ingredients listed below were ground together in the proportions stated to produce a powdered mixture readily dispersible in liquids.

Compound No. 10 of Table l 50 Dispersol T (DispersoP is a Trade Mark) 5 China Clay 45 EXAMPLE 45 ish Standard mesh sieve, size 44l00 to obtain the desired size of grains.

/1 wt. Compound No. l l of Table l 50 Dispersol T 12.5 Calcium Iignosulphonate 5 Sodium dodeeylhcnzcnesulphonate 12.5 Sodium acetate 20 EXAMPLE 46 A composition suitable for use as a seed dressing was prepared by mixing all three of the ingredients set out below in the proportions stated.

7( wt. Compound No. 12 of Table l Mineral Oil 2 China Clay l8 EXAMPLE 47 A granular composition was prepared by dissolving the active ingredient in a solvent, spraying the solution obtained on to the granules of pumice and allowing the solvent to evaporate.

wt. Compound No. 22 of Table l 5 Pumice Granules EXAMPLE 48 An aqueous dispersion formulation was prepared by 

1. A METHOD OF COMBATING MOLLUSCS WHICH COMPRISES APPLYING TO SAID MOLLUSCS A MOLLUSCICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 2. The method of claim 1 wherein the compound is 